Dry-cleaning detergent composition



2,941 ,952 Patented June 21, 1930 United States Patent DRY-CLEANING DETERGENT COMPOSITION John T. Lewis, Dayton, and Lloyd E. Weeks, Union, Ohio, assignors to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing. Filed Dec. 3, 1956, Ser. No. 625,604

11 Claims. (Cl. 252-161) The present invention relates to a dry-cleaning process and to dry-cleaning detergent compositions, and particularly to specific combination compositions characterized by high detersive efiiciency .when used in nonaqueous, dry-cleaning solvents. It is 'an object of the invention to provide a detergent composition which possesses stability against the seperation of water which has been emulsified into dry-cleaning solvents, such as the hydrocarbon type exemplified by Stoddards solvent or in halogenated solvents such as perchlorethylene. It is another object of the invention to provide concentrated compositions of the essential detergent components in a non-aqueus solvent carrier, which, upon subsequent dilution after shipping to the ultimate consumer, give a readily usable product.

It has been a difi'iculty of prior art detergents when dissolved in volatile, organic dry-cleaning solvents, such as perchlorethylene, naphtha, gasoline, benzene and Stoddards solvent, that the soap-type detergents are ineffective in preventing the redeposition of soil which has been removed from soiled garments. In the convent-ional dry-cleaning operation, the solvents are continuously or periodically filtered in order to remove accumulated soil. However, it has often been found that the soil which is in suspension, prior to such removal, is quite readily redeposited on other garments, particularly in the cleaning of synthetic fabrics, such as viscose and acetate rayon and nylon. It is, therefore, an object of the present invention to provide a commercial detergent which is characterized in having substantial solubility in a non-aqueous solvent, while at the same time reducing the redeposition property described above.

Another difliculty which has been encountered in the use of prior art detergents in dry-cleaning operations is the separation of the water which has been added to the dry-cleaning solvent. It is common practice to add small proportions of water to the dry-cleaning solvent, which water becomes emulsified with the solvent and aids in the removal of water-soluble stains caused by soluble substances, such as candy and beverages. In connection with 'thispractice, it has been found that'difiiculty is encountered in maintaining the water content of the emulsion at a sufliciently highlevel to be useful, while preventingphase separation from occurring. In the preparation' of a detergent composition to be employed in ,a-

- such as monoethanolamines, diethanolamines, and triethanolamines may similarly be employed.

The condensation products employed in the present invention are prepared by reacting from 2 to 8 moles of an alkylene oxide such as ethylene oxide or propylene oxide per mole of the hydroxyl compound. A' particularly effective compound is obtained when using about 5.6 moles of ethylene oxide. Condensation products may also be employed in which the condensation'is carried out partially With ethylene oxide and partially with propylene oxide, in either order. For example, dodecyl phenol may first be condensed :with three moles of ethylene oxide, followed by 2.6 moles of propylene oxide to obtain a detergent component of particular utility.

The proportion of the condensation product relative to the alkaline salt of the sulfuric acid ester as described above is generally in the range of from to 97% of the said condensation product, and 3% to 30% by weigh-t of the alkaline salt of the type described above.

The concentration of the combination of the condensation product and the alkaline salt of the sulfuric acid ester as employed in liquid dry-cleaning compositions is preferably from 0.25% to 7.0% by Weight relative to the weight of the dry-cleaning liquid, although solutions may be prepared having from 0.25% to by Weight of the active. When concentrates are prepared for ultimate dilution by the consumer, the concentration of the said combination of active components is preferably from 25% to 75% by Weight relative to the weight of the solvent employed.

In the preparation of the said combination compositions, it has been found that a particularly effective detergent for use in a volatile, organic liquid of the drycleaning type may be prepared by condensing from 2 to 8 moles of an alkylene oxide, specifically ethylene oxide or propylene oxide, with a hydroxyl-containing organic compound. Such hydroxyl-containing organic compound preferably has from 8 to 18 carbon atoms, as is exemplified by dodecyl phenol. After the condensation has been formed, a partial sulfiation is carried out to the extent that from 3% to 30% of the final mixture will exist as the neutralized sulfated component. Sulfation of the above condensation product is carried out by treat ing with a proper amount of a sulfating agent, such, for

example, as sulfur trioxide, fuming sulfuric acid or chlorosulfonic acid. Neutralization of the said sulfur ester thus formed is then accomplished by treating the entire reaction mixture with the stoichiometric amount of a basic substance of the group describedabove. However, if it is desired to form the salt of the sulfuric acid ester as a separate preparation, this component and the condensation product may be prepared by separate reactions and the two components then mixed to obtain the dry-cleaning detergent composition. This composi tion is then dissolved in a dry-cleaning solvent to give a concentrate preferably having from 25% to 75% by weight of the said combination detergent together with from 25% to 75% by weight of the dry-cleaning 'so1-- vent. If desired, the said combination may, however, be dissolved directly in the proper amount of dry-cleaning solvent to obtain a mixture containing from 0.25% to 7.0% by weight.

Other synthetic, organic detergent components may supplement the above-described component. A preferred type-of. supplementary detergent componentis the group of allcanolamides of fatty acids, preferably having from tOZZO carbon atoms. type is'thediethanolamide of tall oil fatty acids. Other alkylolamides of tall oil fatty acids may be prepared such asiby the use. of monoor diethanolamine, monoor diisopropanolamine, or 'monoor di-n-propanolamine. Preferred aminesare monoethanolarnine and diethanolamine. Other sources of fatty acids which may be used in the preparation of alkylolamides are the naturally occurring fatty acids, such as those derived from cocoanut oil. The said cocoanut oil fatty, acids are within the present preferred'groupof fatty acids having from 10 to carbon atoms in the acid radical. A desirable compound of this type in the present relationship is lauric d-iethanolamide derived from crude lauric acid and dietlianolaminc.

Another class of auxiliary detergent components are the alkylene polyamines. An example of such a com.- pound is the reaction product of an unsaturated hydrocarbon compound, preferably having from 10 to carbon atoms, condensed with a polyamine, for instance, thereaction product of kerosene with diethylenetriarnine. A preferred. compound of this class is. that obtained by chlorinating propylene tetramer with hypochlorous acid, and then reacting suchproduct with diethylene triamine to. obtain a product having the formula:

Other amines which-may be employed in the preparation of such compounds are ethylene diamine, propylene diamine, dipropylene tn'amine, and triethylene tetramine. The dry-cleaning solvent employed in the present invention is a volatile, organic liquid of the dry-cleaning type, such as Stoddards solvent, naphtha, gasoline, benzene, carbon tetrachloride, trichlorethylene or perchlorethylene.

The following examples illustrate specific embodiments. of the'present invention:

Example 1 A, dry-cleaning detergent composition was prepared by condensing 5.6 moles of ethylene oxide with one mole of dodecyl phenol. This condensation product was then partially sulfated by reaction thereof with chlorosulfonic acid. The resultant sulfuric acid ester was then neutralized by the addition of sodium hydroxide to neutrality to give about 10% by weight of the salt and 90% of the condensation product in the final mixture. This conjointly-formed mixture in the amount of 3 gallons was dissolvedin 150 gallons of Stoddards solvent, corresponding to about 2 weight percent detergent.

Water was also added in an amount corresponding to 70% relative saturation of the air directly over the drycleaning solvent system. By this is meant that theworking solution contains 70% of the amount of Water-which is required completely to saturate the air over the drycleaning solvent containing the dry-cleaning detergent. Detergency tests were then conducted with this detergent solution in a dry-cleaning machine operating with a cycle time of, 15 minutes, with a load of 25 pounds of soiled garmentsof various fibers and colors. Soiled test swatches were added utilizing a synthetic soil of lampblack, tallow and mineral oil (Nujol).

The machine was operated with constant recirculation of the solvents, employing constant filtration through activated carbon as the filter medium. The soiled garments were dry-cleaned, extracted and dried at 160' F. Aftcnthissequence. of operation the dry-cleaned test A preferred compound of this- .4 swatches were measured for soil removal and redeposited by determining the reflectance, and comparing the washed value with the original value. The solvent system was also analyzed to determine the water content, nonvolatiles and also the acid number as an indication of any deterioration of the detergent or pickup of soil that was not retained on the filter.

The composite results obtained in the dry-cleaning of cotton, nylon, viscose, Wool and acetate rayon showed substantially complete removal of soil as determined by reflectance measurements: It-Was found that the 'Water content remained subsequently constant during the drycleaning, and that the water was effectively maintained in emulsion form in the organic solventswithout phase separation. It was also found that the non-volatilc content remained constant during 24 test runs indicating the lack of any precipitation or loss of the detergent during filtration. The acid number also remained substantially constant during 24 test runs showing the stability of the detergent during prolonged use.

Example 2 Thedetergent composition of Example 1 was subjected to, a redepositiontest-in comparison with a commercial dry-cleaningdetergent of the soaptype. This test was conductedby carrying-out a dry-cleaning operation similar to that of Example 1 in a Launderometer, but with the; addition'of unsoiled white worsted swatches of wool which would pickup dispersed soil which had been removed from the; soiled garments. The measurement of whitenesswas-carried out by the use of reflectometer test-MIL-D-lZ, 150-A, QMC, 1953. the percentage retention of whiteness, as a measure of redeposition, in the. use of the'detergent combination of Example. l-was 87.1%, whereas the whiteness obtained utilizingnhessameproportion of soap type dry-cleaning detergentwasonly 75.9%

Detergent compositions of the type described above were also subjected to a dispersion test conducted by storing emulsions of .the dry-cleaning composition containing; an" amount of water'as described in Example 1 abovefor a period of six hours after preparation with soft water-and withwater-having 300 ppm. hardness. At the end of six'hoursuthe compositions were again agitatedrandthe effectiveness of dispersion determined. In this test it was'found that the detergent of Example 1 when present:in4% concentration maintained 100% of its (emulsion) volume for a six hour period, while the samegconcentration of the soap-type dry-cleaning detergent resultedin an emulsion which maintained only Example -3 As an exampleof a-dry-cleaningdetergent composition utilizing; individually-prepared components, a mixture was. prepared as follows:

a Weight percent Dodecyl phenol condensed with 5.6 moles of ethylene oxide 45 Decanoll condensed with; 30. moles of propylene oxide 45 Tridecanol condensed with 1 mole of ethylene oxide,

andf thereafter.sulfated'and neutralized with potassium hydroxide, 10

'The'above: combination was utilizedas a 4.0% solution'; in perchlorethylene andjwas found to give satisfactory results in dry-cleaning.

It was found that Example .4

A dry-cleaning mixture was prepared utilizing the following active components:

Weight percent Dodecyl phonel condensed with 5.6 moles of ethylene oxide 25 Dodecyl phenol condensed with 5 .6 moles of ethylene oxide, and thereafter sulfated and neutralized with sodium hydroxide 8 Diethanolamide of tall oi-l fatty acids 33 Alkylene polyamine obtained by reacting propylene tetramer with hypochlorous acid and then condensing with diethylene triamine 34 The above combination was utilized as the dry-cleaning detergent present in 4% concentration by weight in cleaners naphtha, and was found to give satisfactory results in dry-cleaning operations.

Example 5 A dry-cleaning concentrate was prepared by dissolving 9 pounds of the condensation product of dodecyl phenol condensed with 5.6 moles of ethylene oxide, and 1 pound of the condensation product of dodecyl phenol condensed with 5.6 moles of ethylene oxide and thereafter sulfated and the resultant sulfuric acid ester dissolved in Stoddards solvent and neutralized with sodium hydroxide. The above combination of the two components (90% condensation product and salt) was slowly added to 10 pounds of Stoddards solvent while agitating in order to provide a uniform mixture. This concentrate was found to possess excellent storage stability.

The above concentrate was diluted for use by adding thereto 100 pounds of Stoddards solvent. This diluted working solution was found to give excellent results in dry-cleaning operations such as are described in Example 1.

What is claimed is:

l. A method of dry-cleaning fabric material which comprises contacting it with a detergent composition comprising a volatile, organic liquid of the dry-cleaning type and a mixture containing 70% to 97% by weight of a condensation product of a hydroxyl-containing organic compound having from 8 to 18 carbon atoms condensed with from 2 to 8 moles of an alkylene oxide having from 2 to 3 carbon atoms, and from 3% to 30% by weight of an alkaline sulfate of a condensation product of a hydroxyl-containing organic compound having from 8 to 18 carbon atoms condensed with from 2 to 8 moles of an alkylene oxide having from 2 to 3 carbon atoms.

2. A method of dry-cleaning fabric material which comprises contacting it with a detergent composition comprising a volatile, organic liquid of the dry-cleaning type and a mixture composed with from 70% to 97% by weight of a condensation product of dodecyl phenol with about 5.6 moles of ethylene oxide per mole of the said dodecyl phenol, and from 3% to 30% by weight of the salt of the sulfate of dodecyl phenol condensed with about 5.6 moles of ethylene oxide per mole of the said dodecyl phenol.

3. A method of dry-cleaning fabric material which comprises contacting it with a detergent composition comprising from 93% to 99.75 by weight of a volatile, organic liquid of the dry-cleaning type and from 0.25% to 7% by weight of a combination composed of from 70% to 97% by weight of a condensation product of dodecyl phenol with about 5.6 moles of ethylene oxide per mole of the said dodecyl phenol, and from 3% to 30% by weight of the sodium salt of the sulfate of dodecyl phenol condensed with about 5.6 moles of ethylene oxide per mole of the said dodecyl phenol.

4. A dry-cleaning detergent composition for fabrics Which comprises from 93% to 99.75% by weight of a volatile, organic liquid of the dry-cleaning type, and from 0.25 to 7% by weight of a combination composed of from 70% to 97% by weight of a condensation product of a hydroxyl-containing organic compound having from 8 to 18 carbon atoms condensed with from 2 to 8 moles of an alkylene oxide having from 2 to 3 carbon atoms together with from 3% to 30% by weight of an alkaline salt of the sulfate of a condensation product of a hydroxyl-containing organic compound having from 8 to 18 carbon atoms condensed with from 2 to 8 moles of an alkylene oxide having from 2 to 3 carbon atoms.

5. A dry-cleaning detergent composition for fabrics which comprises from 93% to 99.75% by weight of a volatile, organic'liquid of the dry-cleaning type, and from 0.25% to 7% by weight. of. the combination of from 70% to 97% by weight of a condensation product of a hydroxyl-containing organic compound having from 8 0.25% to 7% by weight of the combination of from 70% to 97% by weight of a condensation product of dodecyl phenol with from 2 to 8 moles of ethylene oxide per mole of the said dodecyl phenol, together with from 3% to 30% by weight of the sodium salt of the sulfate of dodecyl phenol condensed with from 2 to 8 moles of ethylene oxide per mole. of the said dodecyl phenol.

7. A dry-cleaning detergent composition for fabrics which comprises from 93% to 99.75% by weight of a volatile, organic liquid of the dry-cleaning type, and from 0.25% to 7% by weight of the combination of from 70% to 92% by weight of a condensation product of dodecyl phenol with about 5 .6 moles of ethylene oxide per mole of the said dodecyl phenol, together with from 3% to 30% by weight of the sodium salt of the sulfate of dodecyl phenol condensed with about 5.6 moles of ethylene oxide per mole of the said dodecyl phenol.

8. The process for preparing a dry-cleaning, detergent composition for fabrics which comprises condensing from 2 to 8 moles of an alkylene oxide having from 2 to 3 carbon atoms with one mole of a hydroxyl-containing organic compound having from 8 to 18 carbon atoms, and thereafter partially sulfating the said condensation product with a sulfating agent to obtain a sulfuric acid ester, and thereafter neutralizing the said sulfuric ester with an alkali in order to form the alkaline salt of the said sulfuric acid ester, the said alkaline salt being present to the extent of from 3% mixture.

9. The process for preparing a dry-cleaning detergent composition for fabrics which comprises condensing from 2 to 8 moles of an alkylene oxide having from 2 to 3 carbon atoms with one mole of a hydroxyl-containing organic compound having from 8 to 18 carbon atoms, and thereafter partially sulfating the said condensation product of chlorosulfonic acid to obtain a sulfuric acid ester, and thereafter neutralizing the said sulfuric acid ester with an alkali in order to form the alkaline salt of the said sulfuric acid ester, the said alkaline salt being present to the extent of from 3% to 30% by weight in the final mixture.

10. The process for preparing a dry-cleaning detergent composition for fabrics which comprises condensing from 2 to 8 moles of ethylene oxide with dodecyl phenol, and thereafter partially sulfating the said condensation product by sulfating with a sulfating agent, and thereafter neutralizing the resultant sulfuric acid ester with sodium hydroxide in order to form the sodium salt of the said sulfuric acid ester, the said sodium salt being present to to 30% by weight in the final the extent of from 3% to 30% by weight in the final mixture. 7

11. The process for preparing a dry-cleaning detergent composition for fabrics which comprises condensing from 2 to 8 moles of ethylene oxide with dodecyl phenol, and thereafter partially sulfating the said condensation product by sulfating with chlorosulfonic acid, and thereafter neutralizing the resultant sulfuric acid ester Withsodium hydroxide in order to form the sodium saltofthe said sulfuric acid ester, the said sodiumsalt being present to the extent of from 3% to 30% by weight in the final mixture. I

References Citedinthe fileof this patent UNITED STATES PATENTS 2,213,477 Steindorff Sept. 3, 1940 2,395,971 Loder Mar. 5, 1946 2,427,577 Smith Sept. 16, 1947 2,697,075 Echols Dec. 14, I954 2,736,632' Blau Feb. 28, 1956 2,758,977 Knowles et al. Aug. 14,1956

FOREIGN PATENTS 719,445 Great Britain Dec. 1, 1954 729,531 Great Britain May 4, 1955 OTHER REFERENCES Schwartz: Surface Active Agents, Interscience Publishers, Inc., New York (1949), pages vii, viii, 463 and Fulton: Applied Sciencefor Drycleaners, National Institute ofCleaning and Dyeing, Silver Spring, Md. (1951),

page 346. 

4. A DRY-CLEANING DETERGENT COMPOSITION FOR FABRICS WHICH COMPRISES FROM 93% TO 99.75* BY WEIGHT OF A VOLATILE, ORGANIC LIQUID OF THE DRY-CLEANING TYPE, AND FROM 0.25% TO 7% BY WEIGHT OF A COMBINATION COMPRISED OF FROM 70% TO 97% BY WEIGHT OF A CONDENSATION PRODUCT OF A HYDROXYL-CONTAINING ORGANIC COMPOUND HAVING FORM 8 TO 18 CARBON ATOMS CONDENSED WITH FROM 2 TO 8 MOLES OF AN ALKLYLENE OXIDE HAVING FROM 2 TO 3 CARBON ATOMS TOGETHER WITH FROM 3% TO 30% BY WEIGHT OF AN ALKALINE SALT OF THE SULFATE OF A CONDENSATION PRODUCT OF A HYDROXYL-CONTAINING ORGANIC COMPOUND HAVING FROM 8 TO 18 CARBON ATOMS CONDENSED WITH FROM 2 TO 8 MOLES OF AN ALKLENE OXIDE HAVING FROM 2 TO 3 CARBON ATOMS. 